Plasma-Activated Polydimethylsiloxane Microstructured Pattern with Collagen for Improved Myoblast Cell Guidance.

We focused on polydimethylsiloxane (PDMS) as a substrate for replication, micropatterning, and construction of biologically active surfaces. The novelty of this study is based on the combination of the argon plasma exposure of a micropatterned PDMS scaffold, where the plasma served as a strong tool for subsequent grafting of collagen coatings and their application as cell growth scaffolds, where the standard was significantly exceeded. As part of the scaffold design, templates with a patterned microstructure of different dimensions (50 × 50, 50 × 20, and 30 × 30 µm2) were created by photolithography followed by pattern replication on a PDMS polymer substrate. Subsequently, the prepared microstructured PDMS replicas were coated with a type I collagen layer. The sample preparation was followed by the characterization of material surface properties using various analytical techniques, including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). To evaluate the biocompatibility of the produced samples, we conducted studies on the interactions between selected polymer replicas and micro- and nanostructures and mammalian cells. Specifically, we utilized mouse myoblasts (C2C12), and our results demonstrate that we achieved excellent cell alignment in conjunction with the development of a cytocompatible surface. Consequently, the outcomes of this research contribute to an enhanced comprehension of surface properties and interactions between structured polymers and mammalian cells. The use of periodic microstructures has the potential to advance the creation of novel materials and scaffolds in tissue engineering. These materials exhibit exceptional biocompatibility and possess the capacity to promote cell adhesion and growth.

Surface modification of polydimethylsiloxane by the cataractous eye protein isolate.

Polydimethylsiloxane (PDMS), even though widely used in microfluidic applications, its hydrophobic nature restricts its utility in some cases. To address this, PDMS may be used in conjunction with a hydrophilic material. Herein, the PDMS surface is modified by plasma treatment followed by cross-linking with the cataractous eye protein isolate (CEPI). CEPI-PDMS composites are prepared at three pH and the effects of CEPI on the chemical, physical, and electrical properties of PDMS are extensively investigated. The cross-linking between PDMS and the protein are confirmed by FTIR, and the contact angle measurements indicate the improved hydrophilic nature of the composite films as compared to PDMS. Atomic Force Microscopy results demonstrate that the surface roughness is enhanced by the incorporation of the protein and is a function of the pH. The effective elastic modulus of the composites is improved by the incorporation of protein into the PDMS matrix. Measurements of the dielectric properties of these composites indicate that they behave as capacitors at lower frequency range while demonstrating resistive characteristics at higher frequency. These composites provide preliminary ideas in developing flexible devices for potential applications in diverse areas such as energy storage materials, and thermo-elective wireless switching devices.

Solvent Extraction of PDMS Tubing as a New Method for the Capture of Volatile Organic Compounds from Headspace.

Polydimethylsiloxane (PDMS) tubing is increasingly being used to collect volatile organic compounds (VOCs) from static biological headspace. However, analysis of VOCs collected using PDMS tubing often deploys thermal desorption, where samples are considered as 'one-offs' and cannot be used in multiple experiments. In this study, we developed a static headspace VOC collection method using PDMS tubing which is solvent-based, meaning that VOC extracts can be used multiple times and can be linked to biological activity. Using a synthetic blend containing a range of known semiochemicals (allyl isothiocyanate, (Z)-3-hexen-1-ol, 1-octen-3-one, nonanal, (E)-anethol, (S)-bornyl acetate, (E)-caryophyllene and pentadecane) with differing chemical and physicochemical properties, VOCs were collected in static headspace by exposure to PDMS tubing with differing doses, sampling times and lengths. In a second experiment, VOCs from oranges were collected using PDMS sampling of static headspace versus dynamic headspace collection. VOCs were eluted with diethyl ether and analysed using gas chromatography - flame ionization detector (GC-FID) and coupled GC - mass spectrometry. GC-FID analysis of collected samples showed that longer PDMS tubes captured significantly greater quantities of compounds than shorter tubes, and that sampling duration significantly altered the recovery of all tested compounds. Moreover, greater quantities of compounds were recovered from closed compared to open systems. Finally, analysis of orange headspace VOCs showed no qualitative differences in VOCs recovered compared to dynamic headspace collections, although quantities sampled using PDMS tubing were lower. In summary, extraction of PDMS tubing with diethyl ether solvent captures VOCs from the headspace of synthetic blends and biological samples, and the resulting extracts can be used for multiple experiments linking VOC content to biological activity.

PDMS nanoparticles-decorated PDMS substrate promotes adhesion, proliferation and differentiation of skin cells.

Polydimethylsiloxane (PDMS) is known to be a common substrate for various cell culture-based applications. However, native PDMS is not very conducive for cell culture and hence, surface modification via cell adhesion moieties is generally needed to make it suitable especially for long-term cell culture. To address this issue, we propose to coat PDMS nanoparticles (NPs) on the surface of PDMS film to improve adhesion, proliferation and differentiation of skin cells. The proposed modification strategy introduces necessary nanotopography without altering the surface chemical properties of PDMS. Due to resemblance in the mechanical properties of PDMS with skin, PDMS NPs can recreate the native extracellular nanoenvironment of skin on the PDMS surface and provide anchoring sites for skin cells to adhere and grow. Human keratinocytes, representing 95% of the epidermal skin cells maintained their characteristic well-spread morphology with the formation of interconnected cell-sheets on this coated PDMS surface. Moreover, our in vitro immunofluorescence studies confirmed expression of distinctive epidermal protein markers on the coated surface indicating close resemblance with the native skin epidermis. Conclusively, our findings suggest that introducing nanotopography via PDMS NPs can be an effective strategy for emulating the native cellular functions of keratinocytes on PDMS based cell culture devices.

Functionalization of Polydimethylsiloxane with Diazirine-Based Linkers for Covalent Protein Immobilization.

Biomolecule attachment to solid supports is critical for biomedical devices, such as biosensors and implants. Polydimethylsiloxane (PDMS) is commonly used for these applications due to its advantageous properties. To enhance the biomolecule immobilization on PDMS, a novel technique is demonstrated using newly synthesized diazirine molecules for the surface modification of PDMS. This nondestructive process involves a reaction between diazirine molecules and PDMS through C-H insertion with thermal or ultraviolet activation. The success of the PDMS modification is confirmed by various surface characterization techniques. Bovine serum albumin (BSA) and immunoglobulin G (IgG) are strongly attached to the modified PDMS surfaces, and the amount of protein is quantified using iodine-125 radiolabeling. The results demonstrate that PDMS is rapidly functionalized, and the stability of the immobilized proteins is significantly improved with multiple types of diazirine molecules and activation methods. Confocal microscopy provides three-dimensional images of the distribution of immobilized IgG on the surfaces and the penetration of diazirine-based linkers through the PDMS substrate during the coating process. Overall, this study presents a promising new approach for functionalizing PDMS surfaces to enhance biomolecule immobilization, and its potential applications can extend to multimaterial modifications for various diagnostic and medical applications such as microfluidic devices and immunoassays with relevant bioactive proteins.

Surface-segregating zwitterionic copolymers to control poly(dimethylsiloxane) surface chemistry.

The use of microfluidic devices in biomedicine is growing rapidly in applications such as organs-on-chip and separations. Polydimethylsiloxane (PDMS) is the most popular material for microfluidics due to its ability to replicate features down to the nanoscale, flexibility, gas permeability, and low cost. However, the inherent hydrophobicity of PDMS leads to the adsorption of macromolecules and small molecules on device surfaces. This curtails its use in "organs-on-chip" and other applications. Current technologies to improve PDMS surface hydrophilicity and fouling resistance involve added processing steps or do not create surfaces that remain hydrophilic for long periods. This work describes a novel, simple, fast, and scalable method for improving surface hydrophilicity and preventing the nonspecific adsorption of proteins and small molecules on PDMS through the use of a surface-segregating zwitterionic copolymer as an additive that is blended in during manufacture. These highly branched copolymers spontaneously segregate to surfaces and rearrange in contact with aqueous solutions to resist nonspecific adsorption. We report that mixing a minute amount (0.025 wt%) of the zwitterionic copolymer in PDMS considerably reduces hydrophobicity and nonspecific adsorption of proteins (albumin and lysozyme) and small molecules (vitamin B12 and reactive red). PDMS blended with these zwitterionic copolymers retains its mechanical and physical properties for at least six months. Moreover, this approach is fully compatible with existing PDMS device manufacture protocols without additional processing steps and thus provides a low-cost and user-friendly approach to fabricating reliable biomicrofluidics.

Enhancement of protein immobilization on polydimethylsiloxane using a synergistic combination of polydopamine and micropattern surface modification.

Understanding protein interactions at biointerfaces is critical for the improved design of biomaterials and medical devices. Polydimethylsiloxane (PDMS) is used for numerous device applications, and surface modifications can enhance protein immobilization and the response to cells. A multifunctional approach combining topographical and biochemical modifications was applied to PDMS by fabricating 10-20 µm scale patterns onto PDMS surfaces and by coating with polydopamine (PDA). The modifications were confirmed by surface characterization and bovine serum albumin (BSA), fibrinogen (Fg), and fetuin-A (Fet-A) were radiolabeled with 125I. The amounts of protein attached to the surface before and after elution with sodium dodecyl sulfate (SDS) were quantified from single and complex multi-protein solutions to determine protein stability and competitive binding. The PDA coatings were the most stable and capable of immobilizing the highest levels of all proteins. Furthermore, combinations of PDA coatings with the smallest micropatterns provided an additional improvement, enhancing the amount immobilized and the stability. The adsorption of BSA and Fg from plasma demonstrated competitive binding and possible orientation changes, respectively. It was determined that Fet-A, a less studied protein, adsorbed from plasma at low levels, but the adsorption from fetal bovine serum (FBS) was significantly greater, providing important quantification data from radiolabeling that is relevant to many cell culture studies. Overall, combining topography and PDA modification has a synergistic effect on improving protein immobilization. These findings provide new insight on the quantities of proteins bound to PDMS and PDA coatings with implications for cell interactions in various biotechnology and medical applications.

Ratiometric surface-enhanced Raman scattering strategy using gold nanoparticles confined on an ultrathin polydimethylsiloxane grafted gold mirror film substrate for ferbam screening in fruit juice.

BACKGROUND: In surface-enhanced Raman scattering (SERS) detection methods, the intricacies in the synthesis and recognition processes, along with non-uniform substrate morphologies, induce spectral irreproducibility. Metal (gold) nanoparticles (AuNPs) on gold (Au) mirror film configuration along with a ratiometric approach, constitute a potential system to resolve this issue. RESULTS: To acquire a reproducible and stable SERS response, an ultrathin polydimethylsiloxane (PDMS) spacer layer was grafted onto the Au mirror film via a contact heating step. The AuNPs-supported ultrathin PDMS grafted Au mirror film system was extended for ratiometric sensing of ferbam residue in real fruit juice samples. The hydrophobic PDMS localizes the AuNPs, 4-nitrophenol probe, and ferbam to a smaller region on the PDMS-grafted Au mirror film and prevents their spreading and diffusion. The ratiometric SERS response for ferbam target and probe ratio at I1376/I1326 cm-1 was monitored on the AuNPs@PDMS grafted Au mirror film substrate with good linear fitting. A detection limit of 1.09 × 10-8 mol L-1 and a relative standard deviation of 11.90% were obtained. In addition, ferbam residues in grape and orange juice samples were successfully recovered (96.86%-99.76%). SIGNIFICANCE: The AuNPs@PDMS grafted Au mirror film substrate, coupled with ratiometric analysis, showed excellent SERS activity with high sensitivity and reproducibility. The proposed platform can be adequately extended to detect other pesticide types in complex food settings.

Straightforward Cell Patterning with Ultra-Low Background Using Polydimethylsiloxane Through-Hole Membranes.

Micropatterning is becoming an increasingly popular tool to realize microscale cell positioning and decipher cell activities and functions under specific microenvironments. However, a facile methodology for building a highly precise cell pattern still remains challenging. In this study, A simple and straightforward method for stable and efficient cell patterning with ultra-low background using polydimethylsiloxane through-hole membranes is developed. The patterning process is conveniently on the basis of membrane peeling and routine pipetting. Cell patterning in high quality involving over 97% patterning coincidence and zero residue on the background is achieved. The high repeatability and stability of the established method for multiple types of cell arrangements with different spatial profiles is demonstrated. The customizable cell patterning with ultra-low background and high diversity is confirmed to be quite feasible and reliable. Furthermore, the applicability of the patterning method for investigating the fundamental cell activities is also verified experimentally. The authors believe this microengineering advancement has valuable applications in many microscale cell manipulation-associated research fields including cell biology, cell engineering, cell imaging, and cell sensing.

Edge-Functionalized Graphene/Polydimethylsiloxane Composite Films for Flexible Neural Cuff Electrodes.

The design of neural electrodes has changed in the past decade, driven mainly by the development of new materials that open the possibility of manufacturing electrodes with adaptable mechanical properties and promising electrical properties. In this paper, we report on the mechanical and electrochemical properties of a polydimethylsiloxane (PDMS) composite with edge-functionalized graphene (EFG) and demonstrate its potential for use in neural implants with the fabrication of a novel neural cuff electrode. We have shown that a 200 µm thick 1:1 EFG/PDMS composite film has a stretchability of up to 20%, a Young's modulus of 2.52 MPa, and a lifetime of more than 10000 mechanical cycles, making it highly suitable for interfacing with soft tissue. Electrochemical characterization of the EFG/PDMS composite film showed that the capacitance of the composite increased up to 35 times after electrochemical reduction, widening the electrochemical water window and remaining stable after soaking for 5 weeks in phosphate buffered saline. The electrochemically activated EFG/PDMS electrode had a 3 times increase in the charge injection capacity, which is more than double that of a commercial platinum-based neural cuff. Electrochemical and spectrochemical investigations supported the conclusion that this effect originated from the stable chemisorption of hydrogen on the graphene surface. The biocompatibility of the composite was confirmed with an in vitro cell culture study using mouse spinal cord cells. Finally, the potential of the EFG/PDMS composite was demonstrated with the fabrication of a novel neural cuff electrode, whose double-layered and open structured design increased the cuff stretchability up to 140%, well beyond that required for an operational neural cuff. In addition, the cuff design offers better integration with neural tissue and simpler nerve fiber installation and locking.

Enhancing Nasopharyngeal Carcinoma Cell Separation with Selective Fibronectin Coating and Topographical Modification on Polydimethylsiloxane Scaffold Platforms.

The extracellular matrix (ECM) serves as a complex scaffold with diverse physical dimensions and surface properties influencing NPC cell migration. Polydimethylsiloxane (PDMS), a widely used biocompatible material, is hydrophobic and undesirable for cell seeding. Thus, the establishment of a biomimetic model with varied topographies and surface properties is essential for effective NPC43 cell separation from NP460 cells. This study explored how ECM surface properties influence NP460 and NPC43 cell behaviors via plasma treatments and chemical modifications to alter the platform surface. In addition to the conventional oxygen/nitrogen (O2/N2) plasma treatment, O2 and argon plasma treatments were utilized to modify the platform surface, which increased the hydrophilicity of the PDMS platforms, resulting in enhanced cell adhesion. (3-aminopropyl)triethoxysilane and fibronectin (FN) were used to coat the PDMS platforms uniformly and selectively. The chemical coatings significantly affected cell motility and spreading, as cells exhibited faster migration, elongated cell shapes, and larger spreading areas on FN-coated surfaces. Furthermore, narrower top layer trenches with 5 µm width and a lower concentration of 10 µg/mL FN were coated selectively on the platforms to limit NP460 cell movements and enhance NPC43 cell separation efficiency. A significantly high separation efficiency of 99.4% was achieved on the two-layer scaffold platform with 20/5 µm wide ridge/trench (R/T) as the top layer and 40/10 µm wide R/T as the bottom layer, coupling with 10 µg/mL FN selectively coated on the sidewalls of the top and bottom layers. This work demonstrated an innovative application of selective FN coating to direct cell behavior, offering a new perspective to probe into the subtleties of NPC cell separation efficiency. Moreover, this cost-effective and compact microsystem sets a new benchmark for separating cancer cells.

Microchip gas chromatography column using magnetic beads coated with polydimethylsiloxane and metal organic frameworks.

Micro gas chromatography (µGC) using microfabricated silicon columns has been developed in response to the requirement for portable on-site gas analysis. Although different stationary phases have been developed, repeatable and reliable surface coatings in these rather small microcolumns remains a challenge. Herein, a new stationary phase coating strategy using magnetic beads (MBs) as carriers for micro column is presented. MBs modified with organopolysiloxane (MBs@OV-1) and a metal organic framework (MBs@HKUST-1) are deposited in on-chip microcolumns assisted with a magnetic field with an optimized modification process. MBs@OV-1 column showed a minimum HETP of 0.074 cm (1351 plates/m) of 62 cm/s. Mixtures of volatile organic compounds are successfully separated using MBs carried stationary phase which demonstrates that this technique has good chromatographic column efficiency. This method not only provides a novel coating process, washing and characterization of the stationary phases but also establishes a straightforward strategy for testing new absorbent materials for µGC systems.

Stable food grade wax/attapulgite superhydrophobic coatings for anti-adhesion of liquid foods.

Adhesion of liquid foods on their packaging materials has caused significant food wastes and environment pollution, which has attracted great attention. Food grade superhydrophobic coatings are very promising to solve the issue but suffer from low mechanical stability and complex preparation methods. Herein, a food grade superhydrophobic coating for anti-adhesion of liquid foods was prepared by combining edible paraffin wax, polydimethylsiloxane-modified attapulgite natural nanorods and a food grade silicone adhesive. The concentration of polydimethylsiloxane-modified attapulgite, ultrasonication time and the volume ratio of the paraffin wax/attapulgite suspension to the silicone adhesive solution have great influences on wettability and morphology of the coatings. The coatings exhibit good static and dynamic superhydrophobicity due to their hierarchical micro-/nanostructure and low surface energy of the polydimethylsiloxane-modified attapulgite and paraffin wax. Moreover, the coatings exhibit good mechanical and chemical stability. The coatings are also highly repellent towards various liquid foods including the hot ones. Furthermore, the coatings are applicable onto various frequently used flexible and hard food packing materials including polypropylene, polyethylene terephthalate, aluminium alloy and paper, etc. Thus, the superhydrophobic coatings have great application potential in the food packing industry for anti-adhesion of liquid foods.

Disregarded Free Chains Affect Bacterial Adhesion on Cross-Linked Polydimethylsiloxane Surfaces.

The surface properties exhibited by chemically cross-linked polydimethylsiloxanes (CPDMS) such as morphology, stiffness, and wettability have garnered great interest in the study of bacteria-material interactions. Nevertheless, the hidden factor of uncross-linked free PDMS chains that dissociate in CPDMS has often been overlooked when studying the biofilm formation on these polymeric elastomer surfaces. Here, we undertake a comparative characterization of the effects of free chains in CPDMS on bacterial adhesion to both flat and textured Sharklet CPDMS surfaces. Surprisingly, compared to unextracted surfaces, removing free chains from flat and textured CPDMS through solvent extraction results in a tremendous increase in bacterial colony-forming units for both Gram-negative and Gram-positive bacteria up to 2-3 orders in the initial adhesion stage of 2 h. These findings demonstrate that the solvent extraction of free chains from CPDMS is essential in studying the interactions between bacteria and silicone elastomer materials when focusing on a single variable.

Fabrication of Highly Thermally Resistant and Self-Healing Polysiloxane Elastomers by Constructing Covalent and Reversible Networks.

The fabrication of self-healing elastomers with high thermal stability for use in extreme thermal conditions such as aerospace remains a major challenge. A strategy for preparing self-healing elastomers with stable covalent bonds and dynamic metal-ligand coordination interactions as crosslinking sites in polydimethylsiloxane (PDMS) is proposed. The added Fe (III) not only serves as the dynamic crosslinking point at room temperature which is crucial for self-healing performance, but also plays a role as free radical scavenging agent at high temperatures. The results show that the PDMS elastomers possessed an initial thermal degradation temperature over 380 °C and a room temperature self-healing efficiency as high as 65.7%. Moreover, the char residue at 800 °C of PDMS elastomer reaches 7.19% in nitrogen atmosphere, and up to 14.02% in air atmosphere by doping a small amount (i.e., 0.3 wt%) of Fe (III), which is remarkable for the self-healing elastomers that contain weak and dynamic bonds with relatively poor thermal stability. This study provides an insight into designing self-healing PDMS-based materials that can be targeted for use as high-temperature thermal protection coatings.

Printed Directional Bending Sensor with High Sensitivity and Low Hysteresis for Human Motion Detection and Soft Robotic Perception.

We present a high-performance flexible bending strain sensor for directional motion detection of human hands and soft robotic grippers. The sensor was fabricated using a printable porous conductive composite composed of polydimethylsiloxane (PDMS) and carbon black (CB). The utilization of a deep eutectic solvent (DES) in the ink formulation induced a phase segregation between the CB and PDMS and led to a porous structure inside the printed films after being vapored. This simple and spontaneously formed conductive architecture provided superior directional bend-sensing characteristics compared to conventional random composites. The resulting flexible bending sensors displayed high bidirectional sensitivity (gauge factor of 45.6 under compressive bending and 35.2 under tensile bending), negligible hysteresis, good linearity (>0.99), and excellent bending durability (over 10,000 cycles). The multifunctional applications of these sensors, including human motion detection, object-shape monitoring, and robotic perceptions, are demonstrated as a proof-of-concept.

Conformal Hydrogel-Skin Coating on a Microfluidic Channel through Microstamping Transfer of the Masking Layer.

Poly(dimethylsiloxane) (PDMS) is used in microfluidics owing to its biocompatibility and simple fabrication. However, its intrinsic hydrophobicity and biofouling inhibit its microfluidic applications. Conformal hydrogel-skin coating for PDMS microchannels, involving the microstamping transfer of the masking layer, is reported herein. A selective uniform hydrogel layer with a thickness of ∼1 µm was coated in diverse PDMS microchannels with a resolution of ∼3 µm, maintaining its structure and hydrophilicity after 180 days (6 months). The wettability transition of PDMS was demonstrated through the switched emulsification in a flow-focusing device (water-in-oil [pristine PDMS] to oil-in-water [hydrophilic PDMS]). A one-step bead-based immunoassay was performed to detect the anti-severe acute respiratory syndrome coronavirus 2 IgG using a hydrogel-skin-coated point-of-care platform.

Hydrogel-Assisted Double Molding Enables Rapid Replication of Stereolithographic 3D Prints for Engineered Tissue Design.

Tissue-engineered in vitro models are an essential tool in biomedical research. Tissue geometry is a key determinant of function, but controlling the geometry of microscale tissues remains challenging. Additive manufacturing approaches have emerged as a promising means for rapid and iterative changes in the geometry of microdevices. However, it has been shown that poly(dimethylsiloxane) (PDMS) cross-linking is often inhibited at the interface of materials printed with stereolithography. While approaches to replica mold stereolithographic three-dimensional (3D) prints have been described, these methods are inconsistent and often lead to print destruction when unsuccessful. Additionally, 3D-printed materials often leach toxic chemicals into directly molded PDMS. Here, we developed a double molding approach that allows precise replication of high-resolution stereolithographic prints into poly(dimethylsiloxane) (PDMS) elastomer, facilitating rapid design iterations and highly parallelized sample production. Inspired by lost wax casting, we used hydrogels as intermediary molds to transfer high-resolution features from high-resolution 3D prints into PDMS, while previously published work focused on enabling direct molding of PDMS onto 3D prints through the use of coatings and post-cross-linking treatments of the 3D print itself. Hydrogel mechanical properties, including cross-link density, predict replication fidelity. We demonstrate the ability of this approach to replicate a variety of shapes that would be impossible to create using photolithography techniques traditionally used to create engineered tissue designs. This method also enabled the replication of 3D-printed features into PDMS that would not be possible with direct molding as the stiffness of these materials leads to material fracture when unmolding, while the increased toughness in the hydrogels can elastically deform around complex features and maintain replication fidelity. Finally, we highlight the ability of this method to minimize the potential for toxic materials to transfer from the original 3D print into the PDMS replica, enhancing its use for biological applications. This minimization of the transfer of toxic materials has not been reported in other previously reported methods describing replication of 3D prints into PDMS, and we demonstrate its use through the creation of stem cell-derived microheart muscles. This method can also be used in future studies to understand the effects of geometry on engineered tissues and their constitutive cells.

Determination of gas-polydimethylsiloxane distribution constants of major Cannabis terpenes and terpenoids by capillary gas-liquid chromatography.

Terpenes and terpenoids are the principal responsible for the aroma of Cannabis, playing an important role in the interaction with the environment. Analytical determination of these compounds can be done by headspace coupled to solid phase micro-extraction (HS-SPME) and then injected in a gas chromatograph. In the present study, we determined distribution constants between gas and polydimetylsiloxane (PDMS), a conventional SPME liquid phase, at three temperatures between 303.15 and 343.15 K for major Cannabis terpenes and terpenoids employing a method based in gas chromatography using four capillary columns for monoterpenes and five columns for sesquiterpenes. In addition, van't Hoff regressions (logKfg vs T-1) were obtained in order to estimate logKfg at 298.15 K aiming to compare with bibliographic values (experimental or estimated ones). An excellent agreement was found between them. The method, based on chromatographic theory is robust and relatively simple. It is expected that the herein obtained data could be useful for selecting SPME fiber type and dimensions, estimating extraction efficiencies, as well as to develop prediction models and validate them.

Design, analysis and fabrication of solid polymer microneedle patch using CO2 laser and polymer molding.

Microneedle-based transdermal drug delivery into the skin has gained attraction for the past few years. An affordable and effective fabrication methodology is required for the development of micron size needle. Manufacturing cost-effective microneedle patches in batch production is a challenging process. In this work, we proposed a cleanroom-free technique for fabrication of conical and pyramidal geometry of microneedle array for transdermal drug delivery. Using the COMSOL Multiphysics tool, the mechanical strength of the designed microneedle array under axial, bending, and buckling loads for the geometries during skin insertion was investigated. A CO2 laser and polymer molding technique are used to fabricate 10 × 10 designed microneedle array structure. On an acrylic sheet, a designed pattern is engraved to produce a 20 mm × 20 mm sharp conical and pyramidal shape master mold. We successfully created a biocompatible polydimethylsiloxane (PDMS) microneedle patch with an average height of 1200 µm, base diameter of 650 µm, and a tip diameter of 50 µm using acrylic master mold. According to structural simulation analysis, the microneedle array will experience resultant stress that is within a safe range. The mechanical stability of the fabricated microneedle patch was investigated using hardness test and universal testing machine. The depth of penetration studies were performed in an in vitro Parafilm® M model by manual compression tests and its detailed insertion depth was reported. The developed master mold is efficient to replicate several polydimethylsiloxane microneedle patches. The proposed combined method of laser processing and molding mechanism is simple and low-cost for rapid prototyping of microneedle array.